Anthracene dye and process of making same.



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UNITED STATES iatented September 8, 1963 PATENT OFFICE.

MAX H. ISLER, OF MANNHEIM, GERMANY, ASSIGNOR TO THE BADISOHE ANILIN 8a SODA FABRIK, OF LUDW IGSHAFEN-ON-THE-RHINE, BAVARIA, GERMANY, A CORPORATION OF BADEN.

ANT HRACENE DYE AND PROCESS OF MAKING SAME.

SPECIFICATION forming part of Letters Patent No. 738,614, dated September ,8, 1903. Application filed October 16, 1900. Serial No. 33.268. (SpecimensJ To all whom it may concern: Be it known that I, MAX H. ISLER, acitizen of the Swiss Republic, residing at Mannheim,

in the Grand Duchy, of Baden, Germany,

M acid according to the process of German Patout No. 112,115 and which is hereinafter termed .the sult'o-methylene. derivative of diamido-anthraquinone. Now I have discovered that when the so-resulting product is treated with a halogenizing agent a corresponding halogen derivative of the said sulfomethylene derivative results, which halogen derivative on suitable treatment with an aromatic aminsuch as anilin, paratoluidin, &c.and subsequent sulfonation yields my new coloring matter, which dyes wool in shades within the'range of from blue to bluegreen.

The sulfo-methylene derivative of diamidoanthraquinone may be prepared as follows:

Example 1. --Heat a mixture of one hundred (100) kilograms of a ten (10) per cent. paste of l.5-diamido-anthraquinone, three hundred (300) litersof water, ten (10) kilo-.

grams of a forty (40) per cent. solution of formic aldehyde, twenty liters of forty per cent. sodium-bisulfite solution, and

forty (40) liters of fuming hydrochloric acid of thirtymhree (.33) per cent. H01 to sixty degrees centigrade, while stirring until all or almost all of the diamido-anthraqui none has gone into solution, giving a red color. This is eiiected in a comparatively short time. Filter, precipitate the filtrate by means of common salt, press, and dry. My initial material may also be prepared by sub stituting for the 1.5-diamido-anthraquiuone of the preceding example another diamidoanthraqui-none, such as 1.8 or 1.3 diamidoanthraquinone.

In the following examples I further illustrate thenature of my invention and the mannor in which it may be carried into efiect, but

do not wish to be understood as considering it limited to these. The parts are by weight. Example 2-Proclucti0n of abrom'luderiualive of the product of Example 1 in aqueous mixture.The product resulting from Example 1 when employing one hundred kilograms of a ten (10) per cent. paste of 1.5- diamido-anthraquinone is made into a paste with fifteen hundred (1500) liters of water;

and forty-five (45) kilograms of bromin are added and the whole allowed to stand at ordinary temperature until the presenceof the initial material can no longer be shown. ter, precipitate with common salt, press, and yi I Example 3Procluctlon of a bromiu clericatz'ue of the product of Example 1 in glacialacelt'c-ctcid m'lxture.Mix ten (10) kilograms of the dry product of Example 1 with one hundred (100) kilograms of glacial acetic acid and thirty (30) kilograms of bromin.

this mixture for aboutone-half hour. Fil

ter, wash the solid product with glacial acetic acid, and dry.

Example .l-Procluctt'on of a chlom'n clericallice of the product of Example 1.Gradually mix ten (10) kilograms of the dry product of 8c kilograms of concentrated hydrochloric acid (containing thirty-three (33) per cent. H01),

Example 1 with one hundred and fifty and six (6) kilograms of potassium chlorate.

Care should be taken that the temperature. does not rise above thirty (30) or forty (40),

product made from 1.5-diau1ido-anthraquio Fil In place of the,

Boil

none loan only employ the product made from other diamido-anthraquinones, such as specified, and submit them to the action of a halogenizing agent, as illustrated in Exambe obtained which possesses analogous properties.

In the following table I summarize some of the properties of some of my new compounds ples 2, 3, and 4, when a halogen prod u ctwill containing halogen:

Product of Example 1 from 1.5-diamido-an- Product of Example 1 from Product of Example 1 from thraquinone halogenized according to- 1.S-diamido-anthraquinoue 1.S-diamido-anthraquinone halogenized according tohalogenized according to- Properties. Example 2. Example 3. Example 4. Example 2. Example 3. Example 2. Example 3.

Solubility in water. Reddish yel- Insoluble. Insoluble. Partially sol- Insoluble. Partially sol- Insoluble.

lowsolution, uble; conuble; congiving a red tains some tains insoluprecipitate insoluble ble matewith caustic material. rial. soda.

Beha vi r t o w a r d See above. Insoluble. Insoluble. Insoluble. Insoluble. Insoluble. Insoluble.

cold dilute causticsoda solution.

Behavior toward Green color. Brown color. Yellow-brown Green color. R e d d i s h R e d d i s h Y e llo WIS/I1- cold concentrated color. brown color. brown color. brown color. sulfuric acid of 66 Baum Beha vi 0 r t o w a rd Reddish yel- On boiling,red Reddish yel- Reddish yel- Reddish yel- Yellowish-red Yellowish-red ethyl alcohol. low solution. solution. low solution. low solution. low solution. solution. solution.

Behavior toward Atonce,ayel- Atonce,ared; At once, a After two After two After two After two boiling paratoluilow-red 001- in the course brown red; hours, blue. hours, blue. hours, blue. hours, blue. din. or; in the of two hours, aftera long course of blue. boiling, an o n e h o u r olive green. b lu e g b e y o n d that,

green.

By treatment of an aforesaid halogen compound with an aromatic amin and sulfonat- 'ing'this product I arrive at the new coloringmatter, which I particularly desire to protect bythe application for Letters Patent.

Examplefi-Production of new coloringmaiier from the product 0fExampZe-2.Boil a mixture of ten (10) parts of the dried product of Example 2 with one hundred (100) parts of paratoluidin until the melt assumes a blue-green color. This usually takes place in the course of from four (4) to five (5) hours. 0001, add three hundred (300) parts of ethyl alcohol, warm gently until the excess of paratoluidin is dissolved, and filter oif from the new solid product. containssome of my new solid product and maybe recovered from it bydistilling off the alcohol and removing the paratoluidin by meanslo'f dilute hydrochloric acid.

To convert my new product into the sulfovnation product, one (l)part of the well-dried material and from ten to twenty parts of concentrated sulfuric acid of ninety-six (96) percent H 80 are mixed together and stirred for about twelve (12) hours at a temperature of from forty to fifty'(50) de-i grees centigrade; cool, and pour the melt into water, filter, and wash with salt brine until a blue-green shade.

The alcoholic filtrate neutral. The coloring-matter so obtained 40 dyes unmordanted or chrome-mordanted wool In place of .paratolui'din.

in this example I may employ another aromatic amin, such as analin, when an analogous coloring-matter results.

Example ,6-Producti0n of a new coloringmatter from the product of-Ewample 4.Mix ten (10) parts of the product of Example 4 with one hundred (1.00) parts of paratol uidin and boil for from two (2) to three (3) hours. Work up the so-obtained melt in thesame manner as in Example5 and sulfonate in the same manner, when my new coloring-matter likewise-results. In place of paratoluidin in this example I may employ another aromatic amin, such as anilin, when an analogous c01- oring-matter results. In place of the halogen products which can be derived from theproducts resulting from 1.5 diamido-anthraqui- -ucts resulting from another diamido-anthraquinone, such as 1.8 or 1.3 diamido-anthraquinone.

In the following table Lsummarize some of the'properties of the sulfonation productof some of my new coloring-matters.

Sulto-acid obtained from Sulfo-acid obtained from Sulfo {acid obtained Sulfo acid obtained product of Example 1 product of Example 1 from product of Exfrom product of Ex fromLSdiamido-anthrarom1.5diamido-anthraample 1 from 1.3 diample 1 from 1.8-diquinone and halogenized quinone andhalogenized a mid a nthraquia mid o a n t h raquiaccording to Example 2 according to Example 4 none and halogennone and halogenized and this product treated and this product treated iz e d a c c ording to according to Examwith with Example 2 and this ple 3 and thiszproduct p r 0 d u c t treated treated with with- Paratoluidin. Anilin. Paratoluidin. Anilin. Paratoluidin. Paratoluidin.

Agpearance of the dry pow- Ifiligo-like Blue black. Blue black. Blue black. Grayish blue. Blue.

er. ue.

Appearance of the solution Blue green. Pure blue. Blue. Blue. Pure blue. Pure blue.

1D. water.

Behavior toward anilin Blue-green Insoluble. Blue green Insoluble. Green blue solution. Bluish green solusolutlon. solution tion.

. w h c n boiled.

Behavior toward ninety-five- Bluegreen Blu e solu- Blue solu- Bluesolu- Blue solution. Blue solution.

per-cent. ethyl alcohol. solution. tion when tion in the tion when boiled. cold. boiled.

Behavior to ward sulfuric Violet red Cherryred Violet color. Red color. Bluish-red color. Bluish-red color. acid of 66 Baum. color. color.

Behavior toward sulfuric Green color Blue-green Blue green Blue green. Green color. Green color.

acid and boric acid. l on heating. 0 0 l o r o n c o l or o n heating. heating.

Dyes wool U n o r Blue green. Blue green.

danted or c h r o m e morda n t e d b in e g r e e n shade.

My new coloring-matters possess the following genericproperties: They are acid dyes soluble in water, yielding blue to blue-green solutions and which dye wool from the acidbath, giving blue-green to blue shades both when the wool is unmordanted or when it is mordanted with. a chrome-mordant. Upon chemical analysis my new coloring-matter will be seen to contain chlorin or bromin. Now what I claim is- 1. The process forthe production of blue to blue-green coloring-matters of the anthracone, series which consists in treating the rivative of diainido anthraquinone with a halogenizingagent then melting the resulting halogenderivative withaan aromatic amin.

3. The process for the production of coloring-matters of the anthracene series which,

consists intreating the sulfa-methylene derivative of. diamido anthraquinone with a halogenizing agent. i e l l 4:. The'new coloring-matters of the anthracene series such as can be obtained by treat ing the suite-methylene derivative of diamidoan thraquinone with a halogenizing agent and melting the resulting halogen derivative with an aromatic amin, and which when sulfonated dissolve in water or ethyl alcohol giving ablue to blue-green solution, the aqueous solution dyeing wool whether unmordanted or mordanted with chrome giving blue to blue-green shades, and which contain halogen.

5. The coloringmatter which can be obtained by treating the sulfo-methylene derivative of diamido-anthraquinone with a halogenizing agent andmelting the resulting halogen derivative With paratoluidin which in the sulfonated form yields a blue-green to blue solution in water, dyeing unmordantcd or chrome-mordanted wool blue-green shades,

which dissolves in anilin and alcohol yield ing a blue-green to blue solution and in con centrated sulfuric acid yielding a violet-red to bluish-red solution, whose solution in concentrated sulfuric acid to which boric acid has been added is green to blue-green.

In testimony whereof I have hereunto set my hand in the presence of two subscribing 

